Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
  • C07C41/28—Preparation of ethers by reactions not forming ether-oxygen bonds from acetals, e.g. by dealcoholysis
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the invention relates to a process for the preparation of vinyl ethers by splitting off alcohols from acetals / ketals in the presence of heterogeneous catalysts.
• Vinyl ethers are used for the production of special homopolymers and copolymers, which are used in the fields of paint and adhesive production and as auxiliaries in the textile and leather industries. Furthermore vinyl ethers serve as valuable intermediates for organic syntheses e.g. for Diels-Alder reactions, for the production of glutardialdehydes, ⁇ -pyran and ⁇ -picoline as well as active substances.
• vinyl ethers are produced according to Reppe from acetylene and alcohols in the liquid phase with potassium hydroxide as a catalyst.
• the acetylene base is not present everywhere, so an alternative synthesis for vinyl ethers is desirable.
• sulfates such as NaHSO4, sulfates of alkaline earth and heavy metals or alkali / alkaline earth carbonates or CaO (GB 2091-259) on a support material as catalysts.
• These catalysts are basic in nature or the acidity of the support material used is greatly weakened.
• radicals R1 to R3 are, independently of R4, hydrogen and straight-chain or branched alkyl radicals having 1 to 12, in particular 1 to 8, preferably 1 to 4, carbon atoms.
• Suitable alkyl or alkenyl radicals are e.g. Methyl, ethyl, n-propyl, i-propyl, propenyl, i-propenyl, n-butyl, i-butyl, n-butenyl, i-butenyl, pentyl, pentenyl, Hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonenyl, decyl, decenyl, dodecyl or dodecenyl radicals.
• Cycloalkyl radicals are e.g. Cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl or cyclohexenyl radicals.
• Aromatic residues are e.g. Phenyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 2-phenylpropyl, 4-phenylbutyl, 3-phenylbutyl, 2-phenylbutyl or 3-phenylbutenyl radicals, which may be due to the reaction conditions
• Inert radicals such as alkyl radicals or halogen atoms can be substituted.
• Heterocyclic or heteroaromatic residues are, for example, tetrahydrofuran, dihydrofuran, furan, tetrahydrothiophene (thiophane), dihydrothiophene, thiophene, pyridine, thiopyran residues.
• These radicals can also be substituted by radicals which are inert under the reaction conditions, such as alkyl radicals or halogen atoms.
• the radical R4 are alkyl radicals such as methyl, ethyl, n- / i-propyl, propenyl, n, i, t-butyl, butenyl, octyl, octenyl or aralkyl radicals such as benzyl, phenylethyl, Phenylpropylreste or alkylaryl such as toluyl, xylene.
• alkyl radicals such as methyl, ethyl, n- / i-propyl, propenyl, n, i, t-butyl, butenyl, octyl, octenyl or aralkyl radicals such as benzyl, phenylethyl, Phenylpropylreste or alkylaryl such as toluyl, xylene.
• acetals of saturated aliphatic aldehydes e.g. Acetaldehyde, propione or butyraldehyde, pentanal, hexanal and higher homologous n-alkanals such as octanals and decanals, branched aldehydes such as isobutyraldehyde, 2-methylbutanal, 3-methylbutanal, 3,3-dimethylbutanal, 2-methylpentanal, 2-ethylhexanal and 2 -Methyl decanal for use.
• saturated aliphatic aldehydes e.g. Acetaldehyde, propione or butyraldehyde, pentanal, hexanal and higher homologous n-alkanals such as octanals and decanals
• branched aldehydes such as isobutyraldehyde, 2-methylbutanal, 3-methylbutanal, 3,3-dimethyl
• ketones for the ketals used are the following compounds: methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, diisopropyl and diisobutyl ketone, methyl isobutyl ketone, methoxyacetone, cyclopentanone, cyclohexanone, methylcyclopentanone, methylcyclohexanone, cyclohexenone and substituted acetophenone.
• phosphates with a zeolite structure and / or precipitated phosphates of the elements B, Zr, Ce, Fe and / or phosphoric acid or boric acid on support material and / or acidic undoped metal oxides are generally used, in particular used, as catalysts one eg Aluminum phosphates or silicon aluminum phosphates or silicon iron aluminum phosphates or cobalt aluminum phosphate or iron aluminum phosphate or boral aluminum phosphates with zeolite structure, cerium phosphates, zirconium phosphates, boron phosphates, iron phosphates or mixtures thereof.
• Aluminum phosphates synthesized under hydrothermal conditions are used in particular as aluminum phosphate catalysts. These aluminum phosphates have a zeolite structure.
• aluminum phosphates which are produced under hydrothermal conditions, e.g. Use APO-5, APO-9, APO-11, APO-12, APO-14, APO-21, APO-25, APO-31 and APO-33. Syntheses of these compounds are described in EP 132 708, US 4,310,440 and US 4,473,663.
• the AlPO4-5 (APO-5) is synthesized by homogeneously mixing orthophosphoric acid with pseudoboehmite (Catapal SB) in water, adding tetrapropylammonium hydroxide to this mixture and then the mixture at about 150 ° C for 20 to 60 hours under autogenous pressure in one Autoclaves.
• the filtered AlPO4 is dried at 100 to 160 ° C and calcined at 450 to 550 ° C.
• AlPO4-9 (APO-9) is also from orthophosphoric acid and pseudoboehmite, but in aqueous DABCO solution (1,4-diazabicyclo- (2,2,2) octane) at about 200 ° C under autogenous pressure for 200 to 400 h synthesized.
• AlPO4-21 (APO-21) is synthesized from orthophosphoric acid and pseudobeohmit in aqueous pyrrolidone solution at 150 to 200 ° C. under autogenous pressure for 50 to 200 h.
• silicon aluminum phosphates e.g. Use SAPO-5, SAPO-11, SAPO-31 and SAPO-34.
• SAPO-5, SAPO-11, SAPO-31 and SAPO-34 The synthesis of these compounds is described in EP 103 117, US 4,440,871.
• These silicon aluminum phosphates have a zeolite structure.
• SAPO's are produced by crystallization from an aqueous mixture at 100 to 250 ° C. and autogenous pressure for 2 h to 2 weeks, the reaction mixture being reacted from a silicon, aluminum and phosphorus component in aqueous amino-organic solutions.
• These silicon aluminum phosphates have a zeolite structure.
• SAPO-5 for example is obtained by mixing SiO2 - suspended in aqueous tetrapropylammonium hydroxide solution - with an aqueous suspension of pseudoboehmite and orthophosphoric acid and subsequent reaction at 150 to 200 ° C for 20 to 200 hours under autogenous pressure in a stirred autoclave.
• the filtered powder is dried at 110 to 168 ° C and the calcination at 450 to 550 ° C.
• silicon aluminum phosphates e.g. ZYT-5, ZYT-6, ZYT-7, ZYT-9, ZYT-11 and ZYT-12 are suitable.
• the phosphates thus produced can be dried at 100 to 160 ° C., preferably 110 ° C. and calcined at 450 to 550 ° C., preferably 500 ° C., with a binder in a ratio of 90: 10 to 40: 60% by weight. to be formed into strands or tablets.
• Various aluminum oxides, preferably boehmite, amorphous aluminosilicates with an SiO2 / Al2O3 ratio of 25:75 to 90: 5, preferably 75:25, silicon dioxide, preferably highly disperse SiO2, mixtures of highly disperse SiO2 and highly disperse Al2O3 and clay are suitable as binders.
• the extrudates or compacts are dried at 110 ° C / 16 h and calcined at 500 ° C / 16 h.
• Advantageous catalysts are also obtained if the isolated phosphate is deformed directly after drying and is only subjected to calcination after the deformation.
• the phosphates produced can be used in pure form, without binders, as strands or tablets, with extruding or peptizing aids, for example Ethyl cellulose, stearic acid, potato starch, formic acid, oxalic acid, acetic acid, nitric acid, ammonia, amines, silicon esters and graphite or mixtures thereof can be used.
• the phosphate is e.g. Silicon aluminum phosphate, due to the nature of its production, not in the catalytically active, acidic H form before, but e.g. in the Na form, then this can be achieved by ion exchange, e.g. with ammonium ions and subsequent calcination or by treatment with acids completely or partially converted into the desired H form.
• ion exchange e.g. with ammonium ions and subsequent calcination or by treatment with acids completely or partially converted into the desired H form.
• Precipitated aluminum phosphates, B, Fe, Zr, Ce and mixtures thereof can also be used as phosphate catalysts.
• Boron phosphates as catalysts for the process according to the invention can be prepared, for example, by mixing and kneading concentrated boric acid and phosphoric acid and then drying and calcining in an inert gas, air or steam atmosphere at 258 to 650 ° C., preferably 300 to 500 ° C.
• pre-coke By partial coking (pre-coke) it is possible to adjust the activity of the catalyst for an optimal selectivity of the desired reaction product.
• a suitable modification of the catalysts is, for example, that the undeformed or deformed phosphate is doped with metal salts by ion exchange or by impregnation.
• Metals of the 3rd, 4th and 5th main group such as Al, Ga, Ge, Sn, Pb, Ni, transition metals of the 4th to 8th subgroup such as Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, transition metals of the 1st and 2nd subgroups such as Cu, Ag, Zn, rare earth metals such as La, Ce, Pr, Nd, Er, Yb and U used.
• transition metals of the 4th to 8th subgroup such as Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, transition metals of the 1st and 2nd subgroups such as Cu, Ag, Zn, rare earth metals such as La, Ce, Pr, Nd, Er, Yb and U used.
• the doping is expediently carried out in such a way that the deformed phosphate is placed in a riser tube and an aqueous or ammoniacal solution of a halide or a nitrate of the metals described above is passed on at 20 to 100 ° C. (ion exchange).
• ion exchange a further possibility of applying the metal is given by impregnating the phosphate with a halide, a nitrate or an oxide of the above-described metals in aqueous, alcoholic or ammoniacal solution. Both an ion exchange and an impregnation are followed by at least one drying step, optionally a further calcination.
• a possible embodiment is that Cu (NO3) 2 x H2O or Ni (NO3) 2 x 6 H2O or Ce (NO3) 3 x 6 H2O or La (NO3) 2 x 6 H2O or Cs2CO3 is dissolved in water. With this solution, the deformed or undeformed phosphate is soaked for a certain time, about 30 minutes. Any excess solution is freed of water on the rotary evaporator. The impregnated phosphate is then dried at approximately 150 ° C. and calcined at approximately 550 ° C. This impregnation process can be carried out several times in succession in order to set the desired metal content.
• Another possibility for modification consists in subjecting the phosphate - deformed or unshaped - to treatment with acids such as hydrochloric acid, hydrofluoric acid and / or water vapor.
• the procedure is advantageously such that the phosphate, before or after it has been shaped with binders, at from 60 to 80 ° C. for 1 to 3 hours with a 3 to 25% by weight, in particular 12 to 20% by weight, aqueous hydrochloric acid treated.
• the phosphate treated in this way is then washed with water, dried and calcined at 400 to 500.degree.
• a particular embodiment for the acid treatment consists in treating the phosphate with hydrofluoric acid, which is generally used as 0.001 n to 2 n, preferably 0.05 n to 0.5 n, hydrofluoric acid, for example by, before it is deformed at elevated temperature Reflux for 0.5 to 5, preferably 1 to 3 hours.
• the phosphate is expedient at temperatures of 100 to 160 ° C. dried and calcined at temperatures from 450 to 600 ° C.
• the phosphate after being deformed with a binder at elevated temperature, expediently at temperatures of 50 to 90 ° C., in particular 60 to 80 ° C., over a period of 0.5 to 5 hours at 12 to Treated 20% by weight hydrochloric acid.
• the phosphate is then washed out and expediently dried at temperatures from 100 to 160 ° C. and calcined at temperatures from 450 to 600 ° C.
• HF treatment can also be followed by HCl treatment.
• Suitable catalysts are also the acidic undoped oxides of elements of III. and IV. main group and IV. to VI.
• Sub-group of the periodic system in particular oxides such as silicon dioxide in the form of silica gel, diatomaceous earth, furthermore titanium dioxide, zirconium dioxide, phosphorus oxides, vanadium oxides, niobium oxides, boron oxides, aluminum oxides, chromium oxides, iron oxides, molybdenum oxides, tungsten oxides or pumice or mixtures of these oxides. Treatment with acids as described above is one way of modification.
• Catalysts impregnated with phosphoric acid or boric acid can also be used.
• Phosphoric acid or boric acid is supported on SiO2, Al2O3 or pumice or other acidic metal oxides, e.g. applied by impregnation or spraying.
• a phosphoric acid-containing catalyst can be obtained, for example, by impregnating H3PO4 on SiO2 and subsequent drying or calcination.
• phosphoric acid can also be sprayed together with silica gel in a spray tower; this is followed by drying and usually calcination.
• Phosphoric acid can also be sprayed onto the carrier material in an impregnation mill.
• the catalysts described here can be used either as 2 to 4 mm strands or as tablets with 3 to 5 mm diameter or as grit with particle sizes of 0.1 to 0.5 mm or as vortex contact.
• the reaction is advantageously carried out in the gas phase at temperatures from 100 to 500 ° C., in particular from 150 to 350 ° C., at a pressure of 0.1 to 100 bar, in particular 0.5 to 10 bar.
• Reaction in the gas phase can be carried out in a fixed bed or in a fluidized bed. It is also possible to carry out the reaction in the liquid phase (suspension, trickle or bottoms procedure) at temperatures between 50 and 200 ° C.
• the reaction can be carried out batchwise, but preferably continuously. Reduced pressure can be particularly advantageous.
• Non-volatile or solid starting materials are in dissolved form, e.g. used in THF, toluene or petroleum ether solution.
• the starting material can be diluted with such solvents or with inert gases such as N2, Ar, H2O vapor.
• the resulting products are processed using conventional methods, e.g. Distillation from the reaction mixture, isolated; unreacted starting materials are optionally returned to the reaction.
• a particular advantage is obtained if the gaseous reaction products are immediately separated and then broken down into their individual components. Such separation can e.g. be carried out in a fractionation column.
• a preferred embodiment is to carry out the reaction products in an aqueous hydrogen carbonate solution, e.g. KHCO3 or NaHCO3 / Na2SO4 to cool.
• the reactions in the gas phase are carried out under isothermal conditions in a tubular reactor (spiral, 0.6 cm inside diameter, 90 cm length) for at least 6 hours.
• the reaction products are cooled, separated off and characterized by customary methods.
• the quantitative determination of the reaction products and the starting products was carried out by gas chromatography using a known method.
• the catalysts used for the process according to the invention are:
• AlPO4-5 (APO-5) is synthesized by dissolving or suspending 200 g of 98% phosphoric acid and 136 g boehmite in 335 g of water, adding 678 g of a 30% aqueous tetrapropylammonium hydroxide solution and this mixture in a stirred autoclave at 150 ° C in 43 h under autogenous pressure. After filtering off, the crystalline material is dried at 120 ° C. and calcined at 500 ° C. for 16 hours.
• the AlPO4-5 synthesized in this way contains 45.5% by weight Al2O3 and 46.5% by weight P2O5. This material is molded with pseudo boehmite in a mass ratio of 60:40 to 2 mm strands, dried again at 120 ° C. and calcined at 500 ° C. for 16 hours.
• AlPO4-12 (APO-12) is synthesized by dissolving or suspending 200 g of 98% phosphoric acid and 136 g of boehmite in 400 g of water, adding an aqueous solution of 60 g of ethylenediamine and 320 g of H2O and this mixture in one Stirred autoclaves reacted at 200 ° C for 24 h under autogenous pressure. After filtering off, the crystalline material is dried at 120 ° C. and calcined at 500 ° C. for 16 hours.
• the AlPO4-12 thus synthesized contains 55.5% by weight P2O5, 39.7% by weight Al2O3. This material is shaped into 3 mm strands with extrusion aids, dried again at 120 ° C. and calcined at 500 ° C. for 6 hours.
• Silicon aluminum phosphate-5 (SAPO-5) is made from a mixture of 200 g 98% phosphoric acid, 136 g boehmite, 60 g silica sol (30%), 287 g tripropylamine and 587 g H2O. This mixture is reacted at 150 ° C for 168 h under autogenous pressure. After filtration, the crystalline product is dried at 120 ° C and calcined at 500 ° C / 16 h. SAPO-5 contains 49.8 wt.% P2O5, 33.0 wt.% Al2O3, 6.2 wt.% SiO2. SAPO-5 is formed into 3 mm strands with an extrusion aid, dried again at 120 ° C. and calcined at 500 ° C.
• BPO4 is produced by combining 49 g H3BO3 with 117 g H3PO4 (75%) in a kneader, evaporating excess water and shaping the reaction product into 3 mm strands. These strands are dried at 100 ° C and calcined at 350 ° C. Catalyst E contains 8.77% by weight B and 28.3% by weight P.
• CePO4 is obtained by precipitation from 52 g Ce (NO3) 3 x 6 H2O and 56 g NaH2PO4 x 2 H2O. After filtration, the material is shaped into strands, dried at 120 ° C and calcined at 450 ° C. Catalyst F contains 17.1% by weight of Ce and 12.7% by weight of P.
• CZP 100® Commercially available zirconium phosphate (CZP 100®) is shaped into 2 mm strands with shaping aids, dried at 110 ° C. and calcined at 500 ° C./16 h.
• SiO2 commercially available as D 11-10®.
• D 10-10 is impregnated with H3BO3, dried at 110 ° C and calcined at 500 ° C / 5 h.
• the catalyst I is composed of 85% Al2O3 and 15% B2O3.
• Catalyst J is obtained by treating D 10-10 Al2O3 with 85% H3PO4 for 30 min, then drying at 130 ° C / 2 h and calcining at 540 ° C / 2 h.
• the P content is 4.9% by weight.
• TiO2 P 25® is shaped into 2 mm strands, dried at 110 ° C and calcined at 500 ° C / 16 h.

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• 1988
  • 1988-02-11 DE DE3804162A patent/DE3804162A1/de not_active Withdrawn
• 1989
  • 1989-02-03 EP EP89101865A patent/EP0327985A1/fr not_active Ceased
• 1990
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